Process for the oligomerization of olefins and a catalyst thereof

ABSTRACT

Olefinic feedstocks may be oligomerized to form desired oligomers containing a preferred configuration which, in the instant case, is a linear product, by utilizing certain catalytic compositions of matter. The particular catalyst composite which will form a higher percentage of linear products comprises a porous support having composited thereon a catalytically effective amount of an iron group metal and a metal of Group IVA of the Periodic Table along with an alkyl aluminum halide and mercaptan. In addition, if so desired, the catalyst composite will also contain in combination therewith an aluminum alkoxy compound and an aluminum halide.

CROSS REFERENCE TO RELATED APPLICATION

This application is a division of my co-pending application Ser. No. 282,721 filed Dec. 12, 1988 and now U.S. Pat. No. 4,935,575.

BACKGROUND OF THE INVENTION

The oligomerization of olefins is known in the art, such oligomerization processes being effected by treating olefinic hydrocarbons with certain catalysts to obtain various oligomers which will find a useful function in the chemical art. One type of catalyst which may be employed for this particular type of reaction comprises a supported metal compound. For example, U.S. Pat. No. 3,562,351 discloses a method for dimerizing olefins utilizing a supported catalyst which has been prepared by impregnating a suitable support with a salt solution of a Group VIII metal followed by a heat treatment in an inert atmosphere at a temperature less than that which is required to form a metal oxide but which will form a complex on the surface of the solid support. Following this, the catalyst is activated by treatment with an organometallic compound. U.S. Pat. No. 3,483,269 describes a catalyst useful for oligomerizing lower olefins which comprises a ζ-allyl nickel halide supported on an acidic inorganic oxide support. If so desired, the support may have been optionally treated with an alkyl aluminum compound. U.S. Pat. No. 3,592,869 also describes a catalyst which is useful for the oligomerization of olefins. A divalent nickel compound and an alkyl aluminum compound are contacted with an olefinic compound. The resulting mixture is then used to impregnate an inorganic refractory oxide support. Another patent, namely U.S. Pat. No. 3,644,564, describes a catalyst for the oligomerization of ethylene which comprises an organo aluminum-free reaction product of a nickel compound which is an atom of nickel in complex with an olefinically unsaturated compound and fluorine-containing ligand. The catalysts are typically formed in situ. U.S. Pat. No. 3,679,772 describes a process for reacting monoolefins with diolefins, the catalyst for such a reaction comprising a complex of (1) nickel, (2) a group VA electron donor ligand such as an organophosphine, (3) a nonprotonic Lewis acid and (4) a reducing agent which itself may be a Lewis acid, all of which are composited on an acidic silica-based support.

U.S. Pat. No. 3,697,617 describes an oligomerization process involving the use of a catalyst comprising a complex of nickel with a chloro-containing electron donor ligand such as chlorodiphenylphosphine combined with a nonprotonic Lewis acid which is capable of forming a coordination bond with nickel and a reducing agent capable of reducing nickel acetylacetonate to an oxidation state less than 2. This complex may be composited on a solid support comprising an acidic silica-based material such as silica-alumina. The Lewis acid and the reducing agent may comprise the same compound as, for example, ethyl aluminum sesquichloride. U.S. Pat. No. 3,663,451 describes a catalyst which is obtained by reacting a transition metal halide such as nickel halide with a carrier to give a carrier-metal bond. This product is then reacted with a ligand such as a phosphine or ketone and finally activated by treatment with an aluminum alkyl or chloro alkyl.

U.S. Pat. No. 3,755,490 describes the polymerization of an olefin utilizing a catalyst comprising nickel, a Group VA electron donor ligand, a Lewis acid, and a reducing agent on a solid acidic silica-based support. U.S. Pat. No. 3,954,668 is drawn to an oligomerization catalyst comprising a nickel compound, a chloro-containing electron donor ligand, or a phosphorus compound, a nonprotonic Lewis acid reducing agent which is capable of reducing nickel acetylacetonate to an oxidation state of less than 2 and which is also capable of forming a coordination bond with a nickel. U.S. Pat. No. 3,170,904 speaks to a catalyst which is useful for polymerization comprising a large surface area metal of Groups VIIA or VIII of the Periodic Table, boron trifluoride etherate, an organometallic compounds of Groups I, II, III or IV or a halo derivative of an organometallic compound of Groups II, III or IV or a hydride of a metal of Groups I, II or III. The large surface area metal which comprises one component of this catalyst is in metallic form as, for example, Raney nickel. If so desired, the catalyst may be composited on a diatomaceous earth carrier. In like manner, U.S. Pat. No. 3,170,906 discloses a catalyst which comprises (A) a carrier-supported nickel or cobalt oxide which has been prepared by impregnating the carrier with the hydroxide, organic acid salt, inorganic acid salt, followed by oxidation in the presence of oxygen or a combination of nitrogen and oxygen; (B) a boron, titanium, zirconium, or vanadium halide; and (C) an alkyl metal or alkyl metal halide. In addition to these patents, British Patent 1,390,530 describes an oligomerization catalyst which has been prepared by thermally pretreating a metal oxide carrier material followed by reacting with a halogen-containing organo-aluminum compound and thereafter in a step-wise fashion, impregnating this product with a divalent nickel or cobalt complex at temperatures ranging from -50° to 150° C.

Several other patents which describe oligomerization or polymerization catalysts which are unsupported in nature or processes include Japanese Patent 5024282 which is drawn to a catalyst containing a Group VIII metal and tin chloride or zinc chloride as well as Japanese Patent 4722206 which describes an unsupported catalyst prepared by mixing a nickel compound, an aluminum organic compound and a tin tetrahalide. U.S. Pat. No. 3,155,642 describes an unsupported catalyst prepared from an alkyl tin compound and aluminum chloride in addition to a nickel or cobalt compound for the polymerization of a dienic compound. U.S. Pat. No. 3,155,642 also describes an unsupported catalyst comprising a nickel carboxylate, a halide of a metal of Group IV or V and an organoaluminum compound containing at least one alkoxy radical, said catalyst being used for the polymerization of cis-1,4-polybutadiene. Likewise, U.S. Pat. No. 3,457,321 describes an unsupported catalyst prepared from a complex organic compound of a metal of Group VIII, a reducing agent and a tin tetraalkyl compound. Furthermore, U.S. Pat. Nos. 3,483,268 and 3,505,425 are also drawn to unsupported catalysts, the former showing a catalyst comprising nickel acetyl acetonate, an organonickel compound, and an activating agent of an aluminum alkyl alkoxide or aluminum trialkyl while the latter is drawn to a process for preparing this catalyst. British Patent 1,123,474 likewise teaches a process for preparing linear dimers using a catalyst comprising a complex organic compound of a metal of a Group VIII and a tin tetraalkyl compound.

In addition to the patents previously discussed another U.S. Pat., namely U.S. Pat. No. 4,757,042, relates to a catalyst for the oligomerization of olefins. The catalyst which is discussed in this patent comprises a complex of nickel or palladium, certain fluoro-organo sulfur ligands and an organo-metallic reducing agent. The fluoro-organo sulfur compounds or ligands comprises either fluoro-organo thiol or fluoro-organo sulfides, these compounds containing from 1 to about 20 fluoro substituents on the organo portion of the ligand. The catalyst is prepared by contacting the fluoro-organo thiol or fluoro-organo sulfide complexing agent with nickel or palladium or a salt thereof in an organic medium. Following this, the fluorothiol nickel or fluorothiol palladium complex is then admixed with a reducing agent to form the desired catalyst.

As will hereinafter be shown in greater detail the oligomerization of olefins to provide products which possess a minimal branching of the resultant chain may be accomplished by treating the olefinic hydrocarbons in the presence of the catalyst of the present invention, said catalyst maintaining its activity and stability, along with an increased amount of linear products at the expense of dior other polysubstituents on the chain, for a relatively lengthy period of time even in the presence of certain impurities or poisons in the feedstock.

BRIEF SUMMARY OF THE INVENTION

This invention relates to a catalytic composite which is useful for the oligomerization of olefinic hydrocarbons. More specifically, the invention is concerned with a catalyst composite and a process for the oligomerization of olefinic compounds, particularly olefinic hydrocarbons, whereby the use of the catalytic composite will result in the obtainment of selective oligomers of the olefinic feed stock.

The term "polymerization" has a relatively broad meaning in the chemical art. Although it is generally referred to as the preparation of relatively high molecular weight polymers, that is polymers possessing molecular weights of greater than 50,000 or more, it may also refer to low molecular weight polymers, that is, polymers possessing molecular weights lower than 50,000. In contradistinction to this, the term "oligomerization" refers to polymeric compounds in which the molecules consist of only a relatively few monomeric units and thus would include dimerization, trimerization or tetramerization.

Many olefinic hydrocarbons which contain from 4 up to about 12 carbon atoms or more in the chain may be utilized in various industries in many ways. For example, dimers of propylene may be used to improve the octane number of motor fuels which are utilized in internal combustion engines using gasoline as the fuel thereof. The octane number of the fuel will be improved to a level which is high enough, thus enabling the gasoline to be utilized in these combustion engines in an unleaded state. Other olefinic oligomers may also be used for other purposes as, for example, the dimerization product of butene, in which the dimer which is produced during the oligomerization reaction possesses a relatively straight chain configuration with a minimum of branching as, for example, one methyl substituent on the chain. Such a dimer may be used as an intermediate in the production of plasticizers, said plasticizers, when added to a plastic, will serve to facilitate compounding and improving the flexibility as well as other properties of the finished product. Likewise, a trimer of butene or a dimer of hexene in which the olefin contains 12 carbon atoms may be used as an intermediate in various organic syntheses such as in the preparation of lubricants, additives, flavors, perfumes, medicines, dyes, etc. An important use of straight chain oligomers containing 12 or more carbon atoms is in the preparation of biodegradable detergents which are prepared from linear alkyl benzenes with the increased use of detergents, for washing and cleaning purposes. It is necessary that these detergents, after use, be biodegradable in nature in order to prevent an unwanted buildup of foams which may form on the surface of ponds, lakes, rivers, streams, etc. and which may form a source or supply of potable water for communities. By utilizing an alkyl benzene in which the alkyl chain is substantially linear in nature and which does not contain a high degree of methyl substituents on the chain, it is possible to form a product which is susceptible to attack by microorganisms, these organisms being able to degrade the detergent to a point whereby the compound is substantially destroyed.

It is therefore an object of this invention to provide a catalyst for the oligomerization of olefinic hydrocarbons.

A further object of this invention is to provide a specific catalyst system which may be used in a process for the oligomerization of olefinic hydrocarbons whereby selective oligomers containing a desired configuration may be obtained as a result of this process.

In one aspect an embodiment of this invention resides in a catalytic composite for the oligomerization of olefins comprising a catalytically effective amount of an alkyl aluminum halide compound on a porous support containing a catalytically effective amount of an iron group metal and a metal of Group IVA of the Periodic Table, said catalyst being prepared by the steps of impregnating a porous support with an aqueous solution of an iron group metal salt and a Group IVA metal salt, calcining the impregnated support at a temperature in the range of from about 300° to about 450° C., and thereafter contacting said calcined support with a solution comprising a mixture of an alkyl aluminum halide and a mercaptan.

Another embodiment of this invention is found in a process for the oligomerization of an olefinic hydrocarbon which comprises treating said hydrocarbon at oligomerization conditions in the presence of a catalytic composite comprising a catalytically effective amount of an alkyl aluminum halide compound on a porous support containing a catalytically effective amount of an iron group metal and a metal of Group IVA of the Periodic Table, said catalyst being prepared by the steps of impregnating a porous support with an aqueous solution of an iron group metal salt and a Group IVA metal salt, calcining the impregnated support at a temperature in the range of from about 300° to about 450° C., and thereafter contacting said calcined support with a solution comprising a mixture of an alkyl aluminum halide and a mercaptan, and recovering the resultant oligomers.

A specific embodiment of this invention is found in a catalytic composite for the oligomerization of olefins comprising a catalyic amount of diethylaluminum chloride on a porous support comprising alumina, said support containing a catalytically effective amount of nickel and tin, the catalyst being prepared by the steps of impregnating alumina with an aqueous solution of nickel nitrate and tin chloride, calcining the impregnated support at a temperature in the range of from about 300° to about 450° C. and thereafter contacting said calcined alumina with a solution comprising a mixture of a diethylaluminum chloride and octanethiol.

Another specific embodiment of this invention is found in a process for the oligomerization of butene which comprises treating said butene at a temperature in the range of from about -20° C. to about 200° C. and a pressure in the range of from about 350 to about 1,000 pounds per square inch gauge in the presence of a catalytic composite which has been prepared by impregnating alumina with an aqueous solution of nickel nitrate and tin chloride, calcining the impregnated support at a temperature in the range of from about 300° to about 450° C. and thereafter contacting the calcined support with a solution comprising a mixture of a diethylaluminum chloride and octanethiol, and recovering the resultant oligomers which comprise a mixture of n-octene methylheptene and dimethylhexene.

Other objects and embodiments will be found in the following further detailed description of the invention.

DETAILED DESCRIPTION OF THE INVENTION

As hereinbefore set forth, the present invention is concerned with a catalyst composite which may be utilized for the oligomerization of olefins and to a process which employs the catalyst. Heretofore, the preparation of a catalytic composite which may be used for the polymerization or oligomerization of olefinic compounds was relatively difficult inasmuch as several relatively expensive compounds were required as components of the composite as well as entailing somewhat complicated methods for the manufacture thereof. In contradistinction to this, the catalytic composite of the present invention is relatively easy to prepare and, in addition, employs compounds which are less expensive than the components of the other catalyst. The final catalystic composite of the present invention will possess a high activity and will be stable over a relatively long period of time. In addition to possessing a high activity and stability to effect the desired oligomerization reaction in spite of the presence of impurities which would, under ordinary circumstances, poison or deactivate the catalyst, the catalyst also possesses the ability to enhance the obtention of linear oligomers at the expense of more highly branched isomers.

The particular impurities which are present in the feedstock and which act to deactivate the catalyst, comprise various sulfur compounds such as carbonyl sulfide, hydrogen sulfide; mercaptans such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, etc.; disulfides such as dimethyl disulfide, diethyl sulfide, etc. In addition, other catalyst deactivating impurities such as oxygenates comprising oxygen-containing organic compounds such as alcohols, including methyl alcohol, ethyl alcohol, propyl alcohol, etc.; ethers such as dimethyl ether, diethyl ether, methyl ethyl ether, methyl propyl ether, etc.; aldehydes such as formaldehyde, acetaldehyde; and ketones such as acetone, methyl ethyl ketone, etc. Generally speaking, the impurities may be present in trace amounts such as in a range of from about 0.1 to about 100 ppm of feedstock. However, even these trace amounts of impurities will have a deleterious effect upon the activity and stability of the oligomerization catalysts and thus quickly deactivate the catalyst when these impurities are present.

As was previously stated I have now unexpectedly discovered that the novel catalysts of the present invention which are prepared according to the methods hereinafter set forth in greater detail will exhibit an unexpected resistance to the poisoning effect of the impurities and will in addition enhance the yield of linear products. The dimer products produced by the oligomerization of olefinic hydrocarbons containing from 6 to about 8 carbon atoms will possess a higher percentage of linear compounds than has been obtained when utilizing previous catalysts. While possessing a high percentage of linear compounds the oligomers, particularly the dimers produced hereby, will contain only 1 methyl substituent, the more highly branched oligomers being minority products. The higher percentage of linear and mono-substituted isomers will be obtained at the expense of di-substituted products. Thus, propylene dimers which are produced by the oligomerization of propylene will possess high octane numbers and thus form excellent octane blending components while the butene dimers, due to the linear or minimal branching of the product, will form excellent intermediates in the preparation of plasticizers and detergents.

The catalytic composite of the present invention will comprise a combination of a catalytically effective amount of an alkyl aluminum compound composited on a porous support containing a hydrate of an iron group metal salt and a compound containing a metal of Group IVA of the Periodic Table. In the preferred embodiment of the invention, the iron group metal hydrate will be obtained from a soluble salt of nickel or cobalt such as, for example, nickel nitrate, nickel hydroxide, nickel bromide, nickel chloride, nickel fluoride, nickel acetate, cobaltic chloride, cobaltous acetate, cobaltous ammonium chloride, cobaltous bromide, cobaltous fluoride, cobaltous perchlorate, cabaltous sulfate, etc. The compound containing the Group IVA metal will comprise salts of these metals such as germanium chloride, germanium iodide, germanium fluoride, germanium sulfide, etc.; stannic bromide, stannic chloride, stannic oxychloride, stannic sulfate, lead acetate, lead perchlorate, etc. It is also contemplated within the scope of this invention that these metals may also be used in their elemental form as one component of the catalytic composite of the present invention, although not necessarily with equivalent results.

The porous support upon which the iron group metal hydrate is impregnated will include inorganic metal oxides such as alumina, silica, mixtures of oxides such as alumina-silica, alumina-zirconia-magnesia, etc. or crystalline aluminosilicates which are commonly known as zeolites.

Examples of alkyl aluminum halide compounds which form another component of the catalytic composite will include alkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, dipropyl aluminum chloride, dimethyl aluminum bromide, diethyl aluminum bromide, dipropyl aluminum bromide, dimethyl aluminum iodide, diethyl aluminum iodide, dipropyl aluminum iodide, etc.

Another component which may be present in the catalyst composite of the present invention will comprise an aluminum alkoxy compound which will act as an activator for the catalytic composite. Examples of these aluminum alkoxy compounds will possess the generic formula Al(OR)₃ in which R comprises a lower molecular weight alkyl radical containing from one to about six carbon atoms. Some specific examples of these aluminum alkoxy compounds will include trimethoxy aluminum, triethoxy aluminum, tripropoxy aluminum, triisopropoxy aluminum, tri-n-butoxy aluminum, tri-t-butoxy aluminum, tripentoxy aluminum, trihexoxy aluminum, etc. It is also contemplated within the scope of this invention that the catalytic composite may, if so desired, also contain an aluminum halide compound in place of the aluminum alkoxy compound or in conjunction therewith. Examples of these aluminum halide compounds will include aluminum chloride, aluminum bromide, aluminum iodide, etc.

In addition to the aforesaid components of the catalytic composite the catalyst will contain an additional component comprising an alkyl mercaptan also defined as an alkanethiol. The preferred alkyl mercaptans which are employed along with the activator comprise those mercaptans containing from 2 to about 20 carbon atoms in the alkyl chain, the preferred mercaptans containing from 6 to about 20 carbon atoms. The alkyl portion of the mercaptan compound may comprise either a straight or branched chain compound. Some specific examples of these alkyl mercaptan or alkanethiol compounds which may be employed will include ethyl mercaptan (ethanethiol), propyl mercaptan (propanethiol), isopropyl mercaptan (isopropanethiol), butyl mercaptan (butanethiol), sec-butyl mercaptan (sec-butanethiol), t-butyl mercaptan (t-butanethiol), pentyl mercaptan (pentanethiol), sec-pentyl mercaptan (sec-pentanethiol), the isomeric hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl mercaptans. It is contemplated that the alkyl mercaptans will be present in the catalytic composite in a gram atom of mercaptan sulfur to iron group metal in a range of from about 0.1:1 to about 4:1, the preferred range being from about 1:1 to about 2:1.

It is to be understood that the aforementioned list of components in the final catalytic composite including iron group metal compounds, Group IVA metal compounds, alkyl aluminum halide compounds, aluminum alkoxy compounds, aluminum halide compounds and alkyl mercaptans are only representative of the class of compounds which may be employed to form the novel catalytic composite of the present invention, and that said invention is not necessarily limited thereto.

The oligomerization catalyst of the present invention may be prepared in such a manner so as to provide the finished catalyst with the desired characteristics with regard to the selectivity of olefins obtained by the reaction of an olefinic hydrocarbon in the presence of such catalysts, as well as specificity of the product so obtained. The catalyst composite may be prepared by impregnating a porous support of the type hereinbefore set forth with a simple divalent iron group metal salt such as, for example, nickel nitrate, and a Group IVA metal salt such as tin chloride, preferably from an aqueous solution. Alternatively, the porous support may be impregnated with an aqueous iron group metal salt and the Group IVA metal may be incorporated into the support by any techniques which are well known to those skilled in the art. For example, sols such as tin or germanium sols may be prepared and impregnated into the support by wellknown sol/gel techniques. In any event, after impregnation of the porous support port such as alumina, said impregnation being effected at ambient temperature and atmospheric pressure, the impregnated support is then subjected to a thermal treatment. By varying the temperature of the thermal treatment, it is possible to obtain a catalyst composite which will provide a greater selectivity to dimer products resulting from the oligomerization of the olefin which will be found to be present in greater amounts in contrast to trimer and tetramer products than are obtained when using other conventional oligomerization catalysts. The thermal treatment of the impregnated support is preferably effected in a range of from about 300° C. to about 450° C., the preferred thermal treatment temperature being in a range of from about 340° C. to about 360° C. The thermal treatment or calcination of the catalyst base containing the impregnated Group IVA metal or salt thereof and iron group metal salt in hydrate form will result in a weight loss due to a loss of water of hydration from the metal salt and will result in the formation of a non-stoichiometric hydrogen and oxygen-containing iron group metal compound which may also be referred to as a hydrate of an iron group metal salt. In the preferred embodiment of the invention, the mole ratio of water of hydration to iron group metal following the thermal treatment will be greater than 0.5:1 and preferably in a range of from about 0.5:1 to about 6:1. The thermal treatment of the catalyst base containing the iron group metal compound in the form of a hydrate will usually be effected for a period of time which is less than that required to completely drive of all of the water of hydration.

The thermal treatment or calcination of the catalyst base and the iron group metal salt at temperatures within the range hereinbefore set forth will result in a bonding of the iron group metal to the catalyst base usually by means of a metal-oxygen-base bond, the oxygen portion of the bond being supplied in part by the hydroxyl groups which are present on the surface of the porous support of the type hereinbefore set forth in greater detail.

Following the thermal treatment, the iron group metal and, if so desired, the Group IVA metal impregnated catalyst base is then treated with an alkyl aluminum halide compound and an alkyl mercaptan to activate the catalyst and produce one which possesses maximum activity. In addition, if so desired, the aluminum halide and/or aluminum alkoxy compounds may also be present in this treatment step to provide a catalyst which will maintain its activity in the presence of impurities of the type hereinbefore set forth in greater detail. It is also contemplated within the scope of this invention when treating the catalyst base with the alkyl aluminum halide and alkyl mercaptan that an alkyl aluminum compound such as trimethylaluminum, triethylaluminum, tripropylaluminum, etc. may also be added to the solution in an amount sufficient to react with the reactive mercaptan hydrogen atom, thus leaving the alkyl groups of the latter compound to be present in a quantity sufficient to activate the iron group metal such as nickel or to form the iron group metal complex which is known to be active in oligomerization reactions. The treatment of the impregnated catalyst base with the various compounds is also effected at ambient temperature and atmospheric pressure utilizing a solution of the compounds dissolved in an organic solvent such as benzene, toluene, isomeric xylenes, etc.

The addition of the organic solution, or conversely the addition of the impregnated base to the organic solution, will result in an exothermic reaction and, after thorough admixture, the resulting solution containing the impregnated base is allowed to return to room temperature. The solvent may then be removed by conventional means such as decantation, evaporation, filtration, etc. and the catalyst composite may then be washed with an organic solvent to remove residue or trace portions of unwanted compounds. Thereafter, the catalyst may then be dried by purging with nitrogen, and recovered. In the finished composite, the alkyl aluminum halide compound is present in the composite in a mole ratio in the range of from about 0.05:1 to about 6:1, preferably in a range of from about 0.1:1 to about 1:1, moles of alkyl aluminum halide compound per mole of iron group metal, the latter being present in said composite, on an elemental basis, in an amount in the range of from about 1% to about 20% by weight of the composite, and preferably in an amount in a range of from about 1% to about 10%. In addition, the Group IVA metal will also be present in said composite, on an elemental basis, in an amount in the range of from about 0.1% to about 20% by weight of the composite, and preferably in an amount in the range of from about 1% to about 10%. The alkyl mercaptan will be present in the composite in an amount in the range of from about 0.01:1 to about 4:1 gram atoms of mercaptan sulfur to iron group metal.

As will hereinafter be shown in greater detail, by preparing a catalyst which possesses the various components in the finished composite in mole ratios or weight percent within the ranges hereinbefore set forth, it is possible to selectively oligomerize olefin compounds containing from about 2 to about 6 carbon atoms with a concurrent obtention of desirable isomers in each of the oligomer products. In addition, by utilizing the presence of a metal of the Group IVA of the Periodic Table in the catalyst composite, as well as an aluminum alkoxide compound, it is possible to obtain a catalyst composite which will be more stable, in that it will not deactivate in the presence of the type of impurities hereinbefore set forth in greater detail which may themselves be present in the feedstock, and which may impede or deter the oligomerization reaction of the present invention.

As an example of how the catalyst composite of the present invention may be prepared, a predetermined amount of a porous base such as alumina, silica, silica-alumina, aluminosilicate, etc. which may be in the form of spheres, pellets, rods, etc. may be prepared in an appropriate apparatus such as an evaporator along with an aqueous solution of a hydrate of an iron group metal salt and a Group IVA metal salt. The mixture may be thoroughly admixed and following this, the apparatus heated to form the desired iron group metal and Group IVA metal impregnated base. The impregnated base may then be placed in a heating apparatus such as a tube furnace and treated with air while bringing the catalyst to a temperature of about 250° C. The heating is accomplished at a relatively slow rate and after the determined temperature has been reached, it is maintained thereat for an additional period of time which may range from about 2 to about 4 hours or more in duration. The calcination of the catalyst base is then effected by increasing the temperature to a predetermined level and maintaining thereat for a period of time sufficient to bring the mole ratio of water of hydration present in the iron group metal salt to a determined level which is preferably in an excess of about 0.5:1 moles of water of hydration per mole of iron group metal.

After allowing the calcination to proceed for this predetermined period of time, heating is discontinued and the catalyst base which contains from about 1% to about 20% by weight of iron group metal and from about 0.1% to about 20% by weight of Group IVA metal, is allowed to cool. The cooled base may then be admixed with a solution of an alkyl aluminum halide compound, an alkyl mercaptan and, if so desired, aluminum halide/aluminum alkoxy compounds dissolved in an organic solvent. As previously discussed, the resulting reaction is exothermic in nature and after allowing the heat to dissipate, the resulting admixture is thoroughly stirred and allowed to stand for a period of time which may range from about 1 to about 100 hours or more in duration. At the end of this period, the organic solvent is removed by decantation, filtration, centrifugation, etc. and the solid catalyst is washed to remove any unreacted material. After washing, the catalyst is then dried in an inert atmosphere such as that provided for by the presence of nitrogen, and recovered.

The oligomerization of olefins containing from 2 to about 6 carbon atoms such as ethylene, propylene, butene-2, pentene-1, pentene-2, hexene-1, hexene-2, hexene-3, may then be effected by treating the oligomer in the presence of the catalyst at oligomerization conditions which will include a temperature in the range of from about -20° C. to about 200° C., the preferred range being from about 30° C. to about 100° C., and a pressure in the range of from about 350 to about 1,000 pounds per square inch gauge (psig). The pressure which is utilized may be the autogenous pressure provided for by the feedstock, if in gaseous phase, or, the feedstock may supply only a partial pressure, the remainder of said pressure being provided by the introduction of an inert gas such as nitrogen, helium, argon, etc. into the reaction zone.

It is contemplated within the scope of this invention that the oligomerization process may be effected in either a batch or continuous type operation. For example, when a batch type operation is employed, a quantity of the novel catalyst composite of the present invention may be placed in an appropriate apparatus such as, for example, an autoclave of the rotating, mixing or stirring type. If the olefinic feedstock is in gaseous form, the autoclave is sealed and the feedstock comprising the olefinic hydrocarbon or a mixture of olefinic and paraffinic hydrocarbon or similar carbon atom length is charged to the reactor until the desired operating pressure has been attained. The apparatus is then heated to the desired operating temperature and maintained thereat for a predetermined period of time which may range from about 1 to about 6 hours or more in duration. At the end of this period of time, heating is discontinued and after the apparatus and contents thereof have returned to room temperature, the excess pressure is discharged and the autoclave is opened. The reaction product is recovered, separated from the catalyst by conventional means such as decantation, filtration, centrifugation, etc. and, if so desired, subjected to fractional distillation whereby the various isomers may be separated, one from another, and stored. Conversely, if so desired, the reaction product comprising a mixture of isomers may be recovered and stored per se without separating the various isomeric fractions which are present in the product mixture.

In the event that the olefinic charge stock is in liquid form, it may be charged to the reactor which is thereafter sealed and pressured to the desired operating pressure by the introduction of an inert gas of the type hereinbefore set forth. The remainder of the operating pressure to obtain the desired oligomer product is carried out in a manner similar to that previously described.

When utilizing a continuous method of operation to obtain the desired oligomer products, a quantity of the catalyst composite is placed in an appropriate apparatus. The feedstock comprising the olefinic compound is continuously charged to this reactor which is maintained at the proper operating conditions of temperature and pressure. As in the case of the batch type operation, the desired operating pressure may be provided for by the olefinic hydrocarbon itself or by the addition of a heated inert gas. After passage through the reactor for a predetermined period of time, the reactor effluent is continuously discharged and the reaction product may be recovered and passed to storage or it may be passed to a distillation apparatus whereby separation of the various isomers and oligomers may be effected. Any unreacted olefinic hydrocarbon which is recovered from the reactor effluent may be recycled back to the reactor to form a portion of the feed charge.

Inasmuch as the catalyst composite of the present invention is in solid form, the continuous method of operation for obtaining the desired oligomers of the olefinic hydrocarbons may be effected in various types of operations. For example, in one type of operation, the catalyst is positioned as a fixed bed in the reaction zone and the olefinic feedstock is charged so that is passes over the catalyst bed in either an upward or downward flow. Another type of continuous operation which may be employed comprises the moving bed type of operation in which the catalyst bed and the feedstock are passed through the reaction zone either concurrently or countercurrently to each other. In addition to the fixed or moving bed type of operation, it is also contemplated that the slurry type of operation may be employed, especially when the olefinic hydrocarbon feedstock is in liquid form. When this type of operation is employed, the catalyst is charged to the reactor as a slurry in the olefinic feedstock.

Examples of oligomers of olefinic compounds which may be obtained when utilizing the catalyst composite of the present invention will include n-butene, isobutene, n-hexene, methyl pentene, dimethyl butene, n-octene, the isomeric heptenes, dimethyl hexenes, n-dodecene, the isomeric methyl undecenes, dimethyl decenes, etc. As was previously stated, the oligomer products which are obtained in the process of this invention will comprise, in the main, the dimers of the particular olefinic compound which was employed as the feedstock, thus, for example, when employing ethylene as the feed, the reaction product will comprise mostly C₄ olefins; when employing propylene as the feedstock, the reaction product will comprise mostly C₆ olefins; and when employing butene as the feedstock, the reaction product will comprise mostly C₈ olefins. In addition, as was previously discussed, the dimers produced in the oligomerization process utilizing the catalyst of the present invention will contain a greater amount of linear products than was previously obtained. Thus, the catalyst composite of the present invention will result in products which find particular uses in the finished product.

The following examples are given for purposes of illustrating the novel catalyst composites of the present invention, methods for preparing these composites and a process for utilizing these composites. However, it is to be understood that these examples are merely illustrative in nature and that the present invention is not necessarily limited thereto.

EXAMPLE I

A catalyst of the present invention was prepared by impregnating alumina spheres with an aqueous solution of nickel nitrate hexahydrate and stannic chloride, said solution containing 0.8 g of concentrated nitric acid per 100 g of alumina. The impregnation was effected in a steam-jacketed rotary evaporator in which the mixture was rolled for a period of 0.5 hours at ambient temperature. The evaporator was then heated with steam for a period of 2 hours during which time the aqueous phase was evaporated. The impregnated alumina base was then loaded into a tube furnace and a flow of air at a rate of 600 cc/min. was passed through the alumina base. The base was then brought to a temperature of 250° C. for a period of 3 hours and thereafter the temperature was increased to 400° C. and maintained thereat for an additional period of 2 hours. Following this, heating was discontinued and the impregnated base containing 4.77 weight percent of nickel, 2.75 weight percent of tin and 1.0 weight percent chlorine, was recovered.

After cooling the impregnated alumina the base was then activated by adding a toluene solution containing 2.2 g of tri-sec-butoxy aluminum, 0.6 g of aluminum chloride, 7.25 g of diethylaluminum chloride, 0.3 g of triethylaluminum and 1.2 g of iso-octanethiol per 100 cc of base, the activation of the alumina base being effected in a glove box under a nitrogen atmosphere. The addition of the activator solution was accomplished by slowly adding the solution over a period of 15 minutes, heat being evolved during this addition due to the exothermic nature of the reaction. Upon completion of the addition of the activator solution the flask was intermittently swirled over a period of 12 hours at the end of which time the solvent was decanted and the catalyst composite was washed with 6 portions of isopentane utilizing 100-150 cc per wash. The resulting catalyst composite was then allowed to dry by evaporation of the excess isopentane while maintaining a nitrogen atmosphere in the glove box.

EXAMPLE II

In a like manner a comparative catalyst which did not contain a mercaptan component was prepared by impregnating an alumina base with an aqueous solution of nickel nitrate hexahydrate and stannic chloride dihydrate, said solution containing 0.8 cc of concentrated nitric acid per 100 g of alumina. The impregnation was effected in a steam-jacketed rotary evaporator to allow the evaporation of the water present in the solution. The impregnated base was placed in a tube furnace and treated in a manner similar to that set forth in Example I above, the finished calcined support containing 4.57 weight percent nickel, 2.25 weight percent tin and 0.89 weight percent chlorine after calcination.

The activation of the catalyst base was effected by placing the base covered with toluene in a glove box and slowly adding thereto a toluene solution containing 2.0 g of tri-sec-butoxy aluminum, 7.25 g of diethyl aluminum chloride per 100 cc of base during a period of 15 minutes to prevent overheating of the catalyst base due to the exothermic nature of the reaction. After intermittently swirling the mixture for a period of 12 hours the toluene was decanted and the catalyst composite was washed with 6 portions of isopentane. The catalyst composite was allowed to dry in the glove box under a nitrogen atmosphere until it was free flowing in nature.

EXAMPLE III

The catalysts which were prepared in accordance with Examples I and II above were utilized in the oligomerization of a butene feed. The oligomerization was effected by placing 50 cc of each catalyst in tubular reactors having an inner diameter of 0.5". The feedstock which comprises 71.2 weight percent of n-butene and 28.8 weight percent of n-butane along with 3 ppm of dimethyldisulfide was charged to the reactor which was maintained at a temperature of 70° C. and a pressure of 700 psig at a rate of 40 g per hour. The oligomerization was effected for a period of 40 hours and the product analyzed. The results of the runs in which Catalyst A was the catalyst of the present invention prepared in Example I and Catalyst B is a comparison catalyst prepared according to Example II are set forth in Table 1 below.

                  TABLE 1                                                          ______________________________________                                                        Catalyst A Catalyst B                                           Isomer         % of Dimer % of Dimer                                           ______________________________________                                         n-octene       16         13                                                   Methylheptene  66         65                                                   Dimethylhexene 18         22                                                   ______________________________________                                    

It is to be noted that when using Catalyst A the increase in the amount of n-octene which was obtained during the run is at the expense of the dimethyl hexene which was formed during the run. 

I claim as my invention:
 1. A catalytic composite for the oligomerization of olefins comprising a catalytically effective amount of an alkyl aluminum halide compound on a porous support containing a catalytically effective amount of an iron group metal and a metal of Group IVA of the Periodic Table, said catalyst being prepared by the steps of impregnating a porous support with an aqueous solution of an iron group metal salt and a Group IVA metal salt, calcining the impregnated support at a temperature in the range of from about 300° to about 450° C., and thereafter contacting said calcined support with a solution comprising a mixture of an alkyl aluminum halide and a mercaptan.
 2. The catalytic composite as set forth in claim 1 in which said iron group metal is present in said composite, on an elemental basis, in an amount in the range of from about 1% to about 20% by weight of said composite.
 3. The catalytic composite as set forth in claim 1 in which said alkyl aluminum halide is present in said composite in a mole ratio of alkyl aluminum halide to iron group metal in a range of from about 0.05:1 to about 6:1 moles.
 4. The catalytic composite as set forth in claim 1 in which the weight ratio of Group IVA metal to iron group metal is in a range of from about 0.1:1 to about 10:1.
 5. The catalytic composite as set forth in claim 1 in which said mercaptan is present in said composite in a gram atom mercaptan sulfur to iron group metal ratio in a range of from about 0.1:1 to about 4:1.
 6. The catalytic composite as set forth in claim 1 in which said mercaptan contains from 2 to about 20 carbon atoms.
 7. The catalytic composite as set forth in claim 6 in which said mercaptan is octanethiol.
 8. The catalytic composite as set forth in claim 6 in which said mercaptan is hexanethiol.
 9. The catalytic omposite as set forth in claim 6 in which said mercaptan is decanethiol.
 10. The catalytic composite as set forth in claim 1 in which said iron group metal is iron.
 11. The catalytic composite as set forth in claim 1 in which said iron group metal is nickel.
 12. The catalytic composite as set forth in claim 1 in which said Group IVA metal is tin.
 13. The catalytic composite as set forth in claim 1 in which said Group IVA metal is germanium.
 14. The catalytic composite as set forth in claim 1 in which said alkyl aluminum halide is diethyl aluminum chloride.
 15. The catalytic composite as set forth in claim 1 in which said alkyl aluminum halide is dimethyl aluminum chloride.
 16. The catalytic composite as set forth in claim 1 in which said porous support comprises alumina.
 17. The catalytic composite as set forth in claim 1 in which said porous support comprises silica.
 18. The catalytic composite of claim 1 further characterized in that said calcined support is additionally contacted with an aluminum alkoxy compound.
 19. The catalytic composite as set forth in claim 18 in which said aluminum alkoxy compound is tri-t-butoxy aluminum.
 20. The catalytic composite as set forth in claim 18 in which said aluminum alkoxy compound is tri-sec-butoxy aluminum.
 21. The catalytic composite of claim 1 further characterized in that said calcined support is additionally contacted with an aluminum halide.
 22. The catalytic composite as set forth in claim 21 in which said aluminum halide is aluminum chloride.
 23. The catalytic composite as set forth in claim 21 in which said aluminum halide is aluminum bromide.
 24. The catalytic composite of claim 1 further characterized in that said calcined composite is additionally contacted with an alkyl aluminum compound.
 25. The catalytic composite as set forth in claim 24 in which said alkyl aluminum compound is triethyl aluminum. 